Potentiation of fixed coppers and other pesticides containing copper and supplementing plant nutrition

ABSTRACT

A pesticide composition includes at least one biologically inert carrier; and at least one ferrite or at least one doped component including at least one fixed copper compound doped with at least one compound selected from the group consisting of iron compounds, zinc compounds, magnesium compounds, calcium compounds, and combinations and/or mixtures thereof. In one embodiment, the doped component has a particle size of about 0.5 nm to about 30 microns. A method for the control of pests includes the step of applying to the pests or their growth habitat the aforementioned composition. The method also includes the control of fungal and other diseases in banana plants, by applying the aforementioned composition to their growth habitat in banana plant groves.

RELATED APPLICATIONS

This application is a continuation in part of application Ser. No.14/689,675, filed Apr. 17, 2015, which '675 application is acontinuation-in-part of application Ser. No. 14/674,607 filed Mar. 31,2015, which '607 application is a continuation-in-part of applicationSer. No. 14/625,405, filed Feb. 18, 2015, which applications areincorporated by reference herein and claims benefit therefrom under 35U.S.C. 120. This application and the aforementioned '405 application arebased upon, and claim priority under 35 U.S.C. 119(e) from, provisionalapplication Ser. Nos. 62/002,330 filed May 23, 2014, 62/003,528 filedMay 27, 2014, 62/020,247 filed Jul. 2, 2014, 62/021,819 filed Jul. 8,2014 and 62/094,775 filed Dec. 19, 2014. These applications areincorporated by reference herein.

FIELD OF THE INVENTION

The present invention relates to potentiation of pesticides containingfixed copper in human, agricultural, fungicidal, bactericidal,anti-pathogen and biocidal applications, by increasing the activity ofits biocidal effects, so that less polluting copper is used.

BACKGROUND

All Patents, scientific articles and other documents mentioned hereinare incorporated by reference as if reproduced in full.

During the 2015 Florida Citrus Show in Fort Pierce, Fla., a 2-dayconference, genuine desperation is clearly seen because it is disclosedthat most of Florida is infected with Huang-longbing (HLB) bacteria andthere are no good treatments for this devastating disease which will allbut destroy the Florida citrus industry. See also, Rusnak, “All Hands OnDeck to Save Florida Citrus”, 2015,http://www.growingproduce.com/citrus/insct-disease-update/all-hands-on-deck-to-save-florida-citrus/.Growers were almost crying as they are abandoning their groves, sellingtheir land, pleading with scientists to do something, anything, a stopgap measure. At the scientific presentation, the scientists were at aloss to offer anything substantial at this time. Vague promises weremade 5 years down the line, etc., that they may have something tocounter HLB. Virtually all the growers are hanging on by theirfingernails. Moreover, the mirror image of the situation in Florida isbeing played out in Italy where a similar systemic bacteria is killingcenturies old olive trees. The natural course of both diseases is verysimilar, inescapably progressing to death, and again there are no goodtreatments. Unless a solution is found within 7 years, there will belittle citrus or olive trees in Florida or Italy, respectively.Moreover, with global warming and climate change there will be manyplant pests, insects, bacteria, and fungi extending their range movinginto new territory severely impacting the way of life and the foodsupply of millions.

An example is the devastating Xylellafastidosa infection of olive trees,in Italy, discussed in “XylellaFastidosa: It's Biology, Diagnosis,Control, And Risks” by J. D. Janse and A. Obradovic. This infection isalmost a mirror image of HLB infection of citrus. Xylella infection is abacterium, which inhabits the internal vascular compartment of the olivetree, the xylem, and causes like HLB, plants to dry out, die, leavingshriveled stumps, that are incapable of bearing fruit. See also theDaily Mail, in the published article at “Olive Oil Under Threat FromBacteria Which Is Hitting Hundreds Of Thousands Of Trees In Italy—AndCould Set Prices Soaring” by Hannah Roberts, and “Italian GovernmentUrged To Take Action To Fight Against Olive Tree Epidemic” in Agro News,Jan. 9, 2015. Like HLB, there are few treatments which target theinternal vascular system of olive trees.

HLB disease of citrus is a devastating phloem limited incurablebacterial infection which is decimating/killing the citrus industryworldwide. See, “Novel Bactericides and Application Methods to ControlHuanglongbing Disease of Citrus” which discusses an overview of“inconsequential effect of nutritional treatments on Huanglongbingcontrol, fruit quality, bacterial titer and disease progress” by T. R.Gottwald, J. H. Graham, et al. See also, “Citrus Disease with No Cure isRavaging Florida Groves” Lizette Alvarez, New York Times, whichprovides: “We just need somebody to figure out how we can kill thisbacteria in these trees.” See also, “Citrus Greening Forces FloridaGrowers To Trust A Controversial Savior” Huffington Post 2013/08/30,which discloses that most commercial growers have adopted foliarnutrition as a stop gap method to fend off the inevitable dying of theircitrus trees. See also, “Overview of Citrus Grower Nutritional SprayCompositions” Tim Spann, which discloses “every fertilizer manufacturernow produces their own program of foliar nutrition for HLB.” Furtherdisclosed is the “Maury Boyd cocktail”, which is the originalnutritional foliar spray for HLB disease support.

Copper (II) hydroxide, also known as cupric hydroxide and having thechemical formula Cu(OH)₂, has a wide variety of commercially importantuses, including as a mordant and pigment in dyeing textile and paperfibers, in the preparation of catalysts and other copper compounds, inmarine paints, and in fungicides and bactericides. There are tens ofmillions of pounds of copper hydroxide pesticides, fungicides,bactericides, and biocides used throughout the world yearly, includingabout three million pounds a year in California alone. The Material FactSheet for “Copper Products” in the Organic Resource Guide from theCenter for Environmental Farming Systems, www.cefs.ncsu.edu/newsevents/. . . product06-copperproducts.pdf discloses at page 93 that copper islabeled for use on over 100 crop plants to control fungal and bacterialdiseases. Page 94 discloses a chart labeled “Copper Studies Showing Fairor Good Efficacy.”

As noted in PCT Patent Publication WO 2006028853 A1 of Oberholzer,Method for stabilizing copper hydroxide, Publication date Mar. 16, 2006,the patent literature discloses a variety of processes for thecommercial manufacture of copper (II) hydroxide. U.S. Pat. Nos.2,924,505, 3,428,731, 3,628,920, and RE 24,324 disclose processesinvolving phosphate. U.S. Pat. Nos. 4,490,337 and 4,808,406 discloseprocesses involving carbonate; the latter process provides a productcomprising considerable copper carbonate, in addition to copperhydroxide. U.S. Pat. Nos. 1,800,828, 1,867,357, 2,525,242, 2,536,096 and3,635,668 disclose processes involving ammonia. The processes of U.S.Pat. Nos. 2,525,242 and 2,536,096 involve oxidation of copper metal inthe presence of ammonia and U.S. Pat. No. 4,944,935 discloses a similarprocess substituting ammonium ion for all or part of the ammonia. Theother processes start with a soluble copper salt, typically copper (II)sulfate. U.S. Pat. No. 4,404,169, European Patent Number EP 80226 BI andPCT Patent Publication WO 02/083566 A2 describe processes starting withcopper (II) oxychloride. J. Komorowski-Kulik, Zeszyty, NaukowePolitecnild Sitaskiej, Series: Chemistry 2001, 142, 59-66 discloses aprocess where an aqueous suspension of copper (II) oxychloride iscontacted with aqueous sodium hydroxide in the presence of glycerol asstabilizer. (See PCT Patent Publication WO 2006028853 A1 of Oberholzer,Method for stabilizing copper hydroxide, Publication date Mar. 16,2006). Oberholzer, in U.S. Pat. No. 7,402,296, claims priority from theaforementioned PCT Patent Publication WO 2006028853 A1 of Oberholzer.

Nufarm discloses the history of copper fungicides, the history of copperhydroxide, how copper hydroxide works, how copper works, particle sizeof copper hydroxide fungicide and more information, including abouttheir products Champ® Dry Prill, Champ® Formula 2 Flowable and Champion®WP (See Nufarm Americas Inc., Nufarm Agriculture Division, “The CopperChamps!” ©2002.)

DuPont discloses a similar product, DuPont Kocide Blue Xtra with similarinformation. (DuPont (Australia) Ltd., DuPont™ Kocide Blue Xtra withBioActive Copper® ©02006.) DuPont discloses a bewildering array ofdozens of plant diseases, treated with DuPont™ Kocide® 3000Fungicide/Bactericide, on a multitude of agricultural crops. (E.I.DuPont de Nemours & Company Crop Protection, DuPont™ Kocide® 3000Fungicide/Bactericide, ©2006-2011.)

Copper pesticides, fungicides, and bactericides are extremely toxic tofish and aquatic organisms. (Nufarm Americas Inc., Agt Division, Champ®WG Specimen Label). Runoff from the use of copper fungicides,bactericides and algaecides into waterways, ground water and the groundis a very serious contamination problem well known to those in the art.For example, Scientific American, Mar. 18, 2013, “Fish Cannot Smell InPolluted Waters” by Brian Bienkowski, discloses: “copper is a posterchild for water pollution” said Nathaniel Scholz, an excitology programmanager at the National Oceanic and Atmospheric Administration's (NOAA)Northwest Fisheries Science Center, further noting “copper isintensively used as a pesticide, fungicide . . . it's found in cars, inboat paint, so boatyards are often contaminated, and it's often found inindustrial discharge and near legacy mining operations. It's a rarepollutant that's both agricultural and urban.” Young coho salmon exposedto low levels of copper did not evade predators—cutthroat trout—nearlyas well as unexposed salmon, according to a lab study by Scholz andcolleagues. The problem is “likely to be widespread in many freshwateraquatic habitats” according to a NOAA report. Copper at lowconcentrations targets the neurons that help fish avoid predators, butat higher concentrations, copper impairs their smell for everything.

The Alabama State Water Program, of the Alabama Water QualityInformation System—FAQ results, discloses that agricultural pesticidesare considered a potential source of copper pollution for water, andthat 10 million pounds of copper was used in agricultural fungicides inthe U.S. alone in 1990, “much of the copper is sprayed on plants andtends to accumulate in the immediate soil environment, making itsusceptible to storm water runoff from agricultural operations.”

“The Grower”, Jan. 1, 2012 by Tom Burfield, discloses that “now,producers are growing increasingly anxious about the effect copperbuildup may have on their groves, and they're increasingly afraid thatthe day will come when pathogens display copper resistance.”

U.S. Pat. No. 5,202,353 of Schroth, Iron Enhancement of Copper BasedFungicidal and Bactericidal and Bactericidal Compositions, 1993,discloses that the addition of soluble iron to copper hydroxidefungicide increases activity of the copper hydroxide fungicidebactericide and reverses resistance to copper in vitro. Also, U.S. Pat.No. 5,385,934 of Schroth, Methods for Preventing Precipitation of CopperBased Bactericidal Compositions Containing Iron, 1995, discloses theaddition of an aggregation inhibiting salt to the copper plus ironcompositions to prevent aggregate/or sediment formation upon theaddition of Fe+3 to the composition. Both of Schroth's patents takentogether require five components—a copper hydroxide component or a fixedcopper component, with a dry surfactant, plus a soluble iron component,plus a liquid surfactant, and plus an aggregation inhibitor, salt.Without being limited, held or bound to any particular theory ormechanism of action Applicant believes that because the copper componentand the iron components are separate, the copper hydroxide beinginsoluble, the iron components being both soluble and insoluble, theaggregation inhibitor, the dry surfactant, and the liquid surfactant,the sizes being vastly different, then it follows that the release rateand quantities and bioavailability of copper and iron ions on plantsurfaces is not identical, or regulated, so that each component mayrelease and disperse their ions at different rates compromising thepesticidal, fungicidal, bactericidal and biocidal effects of thecomposition. Moreover, it is complicated to have 5 different separatecomponents, with different solubilities; namely a copper component, ironcomponents, two different surfactants, and the aggregation inhibitingcomponent. Schroth's iron component is soluble, so that when sprayed onplant leaves, would tend to disappear in the rain, and thus be of littlevalue. This compelled Schroth to disclose, for example, page 1463, inthe sentences before discussion, of Lee and Schroth's paper, “in theseexperiments, insoluble ferric oxide was used to replace half of theconcentrations of ferric chloride for the purpose of increasingpersistence.” See Lee, Schroth, et al., “Increased Toxicity ofIron-Amended Copper-Containing Bactericides to the Walnut BlightPathogen Xanthomonascampestrispv. juglandis” Phytopathology, Ecology adEpidemiology, The American Phytopathological Society, 1993, pgs.1460-1465 (referred to herein as “Schroth/Lee”). Phytotoxicity was notedon trees treated with Champion® plus both ferric chloride and ferricoxide, although there was no difference in the efficacy between thesetwo treatments. Page 1464 of Schroth/Lee discloses: “the effect ofcopper-iron mixtures in reducing blight of nuts has not beensignificantly better then copper compounds alone to date” and “whereascopper compounds are very effective in controlling blight of leaves,they have never demonstrated such effectiveness on nuts.” Schroth/Leealso concludes on page 1464, “although the addition of ferric chlorideto fixed copper compounds increases the concentration of free copperions, phytotoxicity has not been observed in the field. However,phytotoxicity occurred when the insoluble ferric oxide was combined withferric chloride. The reasons for this are unknown but probably havesomething to do with the long-term release of iron ions that interactwith the fixed coppers. This surprising result indicates that much workyet has to be done to find the best formulation that will result in thegreatest kill of bacteria over an extended period of time while at thesame time not harming tender walnut tissues.”

“The effect of iron in increasing the efficacy of copper compoundsoffers a new advance in the use of the age-old copper compounds andshould lead to greatly improved control of bacteria such asX.c.juglandis. However, this will greatly depend on both the ecology ofcopper-resistant bacteria and the efficacy of new formulations ineradicating established populations.”

Schroth's/Lee's paper, and Schroth's patents are clearly not enablingfor “new formulations,” taken together with the failure of “persistence”with their soluble irons on plant leaves, and unacceptable phytoxicity.When Schroth/Lee tried to ameliorate the lack of persistence with theaddition of insoluble iron to their soluble iron, their paper in theauthor's own words discloses their invention is unworkable. Their callfor “new formulations” says it all, as well as their statement “muchwork yet has to be done.” Schroth's disclosures have never caught on incommerce because of the complicated nature of their practice andproblems with the release of ions, phytotoxicity, persistence, lack ofactivity, rain fastness and unperfected development.

Jim Graham, Megan Dewdney, in “Comparison of Copper Formulations forControl of Canker on Hamlin Oranges” disclose the testing of 14different dosages of 11 distinct copper formulations. The formulationsrange from insoluble copper compounds, complexes, chelates to solublecopper chelates. No copper treatment was very effective on fruitincidents at harvest. A preferred size for systemic uptake according toGraham is 5 to 10 nm. See Graham, Jim, Novel Bactericides andApplication Methods to Control Disease of Citrus, IV InternationalSymposium of Plant-Pathogenic Bacteria, Guadalajara, Jalisco, Mexico,Sep. 23, 2014, University of Florida, UF-IFAS, especially third pagefrom end, entitled Alternative bactericide must be non-phytotoxic andsystemic. i.e., capable of loading into the phloem via foliarapplication. No insoluble coppers tested by Graham had a particle sizeof 5-10 nanometers, so that none of the compounds of Graham's testingare capable of systemic administration to the plant through the stomata.

Zinc-doped CuO nanocomposites of a specific size are known for use inspecific fields. Eyal Malka et al., (small 2013,DOI:10.1002/smll.201301081, www.small-journal.com) discloses,“eradication of multi-drug resistant bacteria by a novel zinc-doped CuOnanocomposite.” Michal Eshed, et al., (Advanced Functional Materials2014, pp. 1382-1390, www.afm-journal.de) discloses, “a Zn-doped CuOnanocomposite shows enhanced anti-biofilm and antibacterial activitiesagainst Streptococcus mutans compared to nanosized CuO.” They conclude,“the results of the present study further highlight the potential ofthese novel Zn:CuO np's as inhibitors of biofilm within the context ofthe oral niche.” Moreover, Richardson provides, “commercially producedcupric oxide (copper(2) oxide) is ineffective as a fungicide orbactericide due to small surface areas; that is, dissolution times arevery long compared to other basic copper (2) compounds,” see H. WayneRichardson in the “Handbook Of Copper Compounds And Applications” pg.109. This CuO used by Malka and Eshed is the same copper referred byRichardson above. While 30 nm sized Zn:CuO nanocomponents are known,Applicant submits that taken together, biofilm in the oral niche andcoatings of linens and antimicrobial bandages, they do not relate in anyway to agricultural pesticide, and systemic plant protectorants.Moreover the size of 30 nm previously disclosed does not conform toGraham's teaching of 5-10 nm for systemic administration to citrusplants.

Ploss, et al, U.S. Pat. No. 7,105,136 B2, discloses that doping 5 wt %zinc metal into a copper salt composition intended for agriculturalapplications provided enhanced surface adhesion, as in the case ofplants on leaf and fruit surfaces, thereby increasing the duration ofthe plant-protecting effects and also eliminating the expense andenvironmental emissions associated with the re-application of prior artcompositions that would be required to provide the same level ofprotection. Ploss's use of metallic zinc to provide enhanced surfaceadhesion does not teach any advantages with regard to pesticidalcharacteristics per so. For example, zinc is a metal, an element and isinsoluble in water, with a small surface area. Ploss provides noteaching or suggestion that its metallic zinc is pesticidal as “enhancedsurface adhesion” is clearly taught. This is known to those of knowledgeof the art as an “adjuvant.” Exemplary examples of the overwhelmingplethora of agricultural adjuvants are: Nufarm, “Adjuvants ProductGuide” pg 16, and Momentive, Momentive Adjuvants, Silwet and Agrospreadadjuvants. Nufarm's Spraymate bond is a high quality sticker, depositionand retention agent for use with contact or protectant type fungicidesor with contact and ingested insecticides. Spraymate bond increasesadherence of spray droplets by sticking them firmly to target surfaces.This protects pesticides against wash-off by rain or sprinklerirrigation. Spraymate bond also protects chemicals by slowing the rateof degradation immediately after application. Its key benefits are thatit improves spray droplet deposition, retains and protects droplets ontargets, improves the performance and life of protectant fungicides andcontact insecticides. Furthermore, there is a world of differencebetween pure zinc metal, an element, and insoluble pesticidal zinccompounds.

SUMMARY OF THE INVENTION

This invention is directed to a pesticide, fungicidal, bactericidal,anti-pathogen or biocidal composition including a) at least onebiologically inert carrier and; b) at least one doped componentcomprising at least one fixed copper compound, such as copper hydroxide,doped with at least one compound selected from the group consisting ofiron compounds, zinc compounds, magnesium compounds, calcium compounds,and combinations thereof. In a preferred embodiment, the doped componentonly includes iron compounds and/or zinc compounds as the only dopingcompounds. Preferably, the doped component has a particle size of about0.5 nm to 30 microns. The iron compound and/or zinc compound are dopedinto the fixed copper compound, such as copper hydroxide, singly ortogether in combination. In one embodiment a fixed copper compound isdoped with an insoluble iron compound, such as, for example, where thefixed copper compound is copper hydroxide, and wherein the fixed coppercompound is partially substituted by an insoluble iron compound.Optionally, a surfactant may be included in the composition to providefor a more efficacious formulation.

One advantage of Applicant's invention is that the composition includesdoped components that contain both the fixed copper compounds and theiron, zinc, magnesium, and/or calcium compounds combined on the dopedcomponent. The fixed copper compound, such as copper hydroxide, dopedwith the iron compound and/or zinc compound is used in order to providea more cost effective composition with increased activity as compared tocopper hydroxide alone. Therefore, less copper is required with itsresultant reduced runoff, and less pollution derived from copper.Moreover, iron is a plant micronutrient and the present compositionwould supply iron to plants as against copper hydroxide alone. It hasbeen found that heavy use of copper compounds produces iron chlorosis.In addition, copper hydroxide is a pesticide, fungicide/bactericide thatis so well established so that the present invention could beadministered very similarly to the current methods of copper hydroxideadministration with a straight substitution, more or less, except thatthe amount of elemental copper derived from the present invention willbe reduced, as against stand-alone copper hydroxide, to achieve the sameor greater control or pathogen reduction. In one embodiment of thepresent invention, Applicant submits that the present invention may besubstituted for the copper hydroxide in PCT Patent Publication WO2006028853 to Oberholzer. The composition of the present invention alsoreverses resistance to copper so that copper resistant pathogens becomesensitive to copper.

While the Material Data Sheet for Copper Products, page 94, discloses alist of crops with poor results with copper, it is believed thatApplicant's present invention increases the activity of copper withrespect thereto. In one embodiment, Applicant's present invention may beprovided as a pesticide, fungicide, bactericide, anti-pathogen andbiocidal nutrient spray with optional additional micronutrients and/oroptionally macronutrients, so that there would be a combination copperbased pesticide with micronutrients all in one formulation. In anotherembodiment, Applicant's present invention includes an insoluble copperpesticide, fungicide, bactericide, and anti-pathogen and biocidalcapable of systemic uptake by foliar, root and/or trunk injection, and aplant protectorant, dual mode of action, all in one compound.

The prior art teaches various complexes of copper compounds, mixtureswhich are two or more substances that are not chemically combined, andchelates of copper compounds. Compounds of the present invention areoverwhelmingly, compellingly, and persuasively, distinguishable, asdoped zinc compounds and doped iron compounds are internalized in thecopper hydroxide or other fixed coppers. Complexes and chelates arejoined so that they are externalized to the copper hydroxide or otherfixed coppers. Moreover, being externalized to the copper hydroxide orother fixed copper produces larger particulates undesirable for systemicadministration.

Applicant's doped components can also be sized at about 5 nm-10 nm, andother larger particulates, in one embodiment, to provide both plantprotectorant and systemic uptake to be carried internally through theplant phloem and xylem to kill systemic bacterial infections such asHLB, and Xylellafastidosa, and other systemic pathogenic fungi, orinternal pathogens. Applicant's doped composition of fixed coppers dopedwith zinc, iron, or both, are also useful in treating banana plantsafflicted with Black Sigatoka disease, Yellow Sigatoka disease andPanama disease.

The Applicant's invention clearly will not displace and replace theentire world use of pesticides. However, applicant's invention willclearly replace and displace many of the highly toxic pesticidescurrently being used against pests which are resistant to existingcopper pesticides.

Moreover the Applicant's invention will decrease the breadth, depth andrange of pesticides currently resistant to copper pesticides, restoringsensitivity and high activity. Moreover a Google search discloses over52 million hits for the well-known established harmful effects ofpesticides.

Moreover, Wikipedia discloses, “Environmental Impact of Pesticides” withone page and a half of horrific pesticide environmental effects ofclasses of pesticides. In contrast, the Applicant's present inventionreduces the need for the quantity of copper currently being used as apesticide and displaces and replace many current highly toxic poisonouspesticides currently being used. Copper is the lesser of the two evilsas against synthetic agricultural chemical pesticides with theirwell-known toxicities and horrific environmental effects.

BRIEF DESCRIPTION OF THE DRAWINGS

The preferred embodiment of the present invention can best be understoodin connection with the accompanying drawing. It is noted that theinvention is not limited to the precise embodiments shown in drawings,in which:

FIG. 1 is a copy of an X-Ray Diffraction test showing copper hydroxidedoped with 15 at % insoluble iron as a dopant in accordance with oneembodiment of the present invention. There are no additional peaksproving that the iron is incorporated within the copper hydroxide.

FIG. 2 is a transmission electron microscopy (TEM) image of Applicant'siron doped copper hydroxide at 15 at % iron in accordance with oneembodiment of the present invention. The scale on the lower left of FIG.2 shows a comparable length of 50 nm. The size of the iron doped 15 at %Fe copper hydroxide particulates is about 3.5 nm to 9 nm, tested inquadruplicate and by transmission electron microscopy (TEM).

FIG. 3 is an elemental analysis chart demonstrating the presence of bothiron and copper in the iron doped copper hydroxide compound inaccordance with one embodiment of the present invention of FIG. 1 andFIG. 2 above.

FIG. 4 is the X-ray diffraction of 15 at % iron doped copper hydroxidewith an additional 10 at % iron that the copper hydroxide is unable toincorporate, so that the final composition is 15 at % iron doped copperhydroxide+10 at % unincorporated/free iron hydroxide and/or iron oxide.

DETAILED DESCRIPTION OF THE INVENTION

The invention is a pesticide, fungicidal, bactericidal, anti-pathogen orbiocidal composition comprising a) at least one biologically inertcarrier; and b) at least one doped component including at least onefixed copper compound doped with at least one compound selected from thegroup consisting of iron compounds, zinc compounds, magnesium compounds,calcium compounds and combinations thereof. In a preferred embodiment,the doped component only includes iron compounds and/or zinc compoundsas the only doping compound. For example, copper hydroxide may be dopedwith iron hydroxide, iron oxyhydroxide or other iron compound as onedoped component. In one embodiment, the fixed copper compound is dopedwith an insoluble iron compound, wherein the fixed copper compound ispartially substituted by the insoluble iron compound. The invention alsocomprises a fixed copper compound, such as copper hydroxide, doped witha zinc compound. Furthermore, the fixed copper compound, such as copperhydroxide, may be doped with both an iron compound and a zinc compound.Applicant's invention includes at least one doped component containingboth the fixed copper compound doped with an iron compound and/or a zinccompound that can be used similarly to how copper hydroxide alone isused. In one embodiment of the present invention, an iron compound isdoped on copper hydroxide, a zinc compound is doped on copper hydroxide,a zinc compound and an iron compound are doped on copper hydroxide,singly and optionally combined together, and or added to other pesticideagents. The doped component is prepared according to methods describedherein and readily understood to those of skill in the art. Thecomposition can be used in many of the applications that copperhydroxide is currently utilized, and many new pesticidal indicationswhich are currently resistant to copper. See, for example, WO2006028853.In a preferred embodiment, copper hydroxide is doped with iron hydroxideto provide 15 at % iron to the doped component, which results in a blackdoped component. In another preferred embodiment, the atomic percentage(at %) of iron in the doped component is less than 15 at %, morepreferably less than 10 at %. Because of the increased biocidalactivity, the preferred copper hydroxide-iron hydroxide doped componentprepared by the present method is especially useful as an activeingredient in pesticides, fungicides, bactericides and biocides. Thisincreased biocidal activity reduces the number of pathogens currentlyresistant to copper pesticides, increasing the range and breath ofactivity of copper against other bacteria, fungi, viruses, mycoplasma,and other pathogenic organisms.

Preferably, the composition is administered to plants by a methodselected from the group consisting of dusting, sprinkling, spraying,brushing, dipping, smearing, impregnating, injection of the compositioninto plant vasculature, and application to a root system.

DEFINITIONS

In the context of this application, several terms are utilized asfollows:

The definition of “pesticide” used in this application refers to theUnited States EPA definition page 1 of www.epa.gov/agriculture/tpes.htmlwhich is “A pesticide is any substance or mixture of substances intendedfor preventing, destroying, repelling, or mitigating any pest. Pests canbe insects and insect-like organisms, mice and other vertebrate animals,unwanted plants (weeds), or fungi, bacteria and viruses that cause plantdiseases. Though often misunderstood to refer only to insecticides, theterm pesticide also applies to herbicides, fungicides, and various othersubstances used to control pests.”

The definition of a “mixture”: a mixture contains 2 or more substancesthat are not chemically combined. Mixtures are unlike chemicalcompounds, because: the substances in a mixture can be separated usingphysical methods such as filtration and distillation. Mixtures havevariable compositions while compounds have a fixed definite formula.When mixed, individual substances keep their properties in a mixture,while if they form a compound their properties can change. Seehttp://www.chemicool.com/definition/mixture.htm). An example of amixture is NORDOX 30/30 wg, manufactured by NORDOX AS do MontereyAgResources, EPA Reg. No. 48142-7), which is a cuprous oxide and zincoxide mixture.

The definition of “elements” and “compounds”: “Elements and compoundsare pure chemical substances found in nature. The difference between anelement and a compound is that an element is a substance made of thesame type of atoms, whereas a compound is made of different elements indefinite proportions. Examples of elements include iron, copper, zinc,hydrogen and oxygen. Examples of compounds include water (H₂0) and salt(sodium chloride-NaCl).” See,http://www.diffen.com/difference/Comound_vs_Element.

The definition of “complex”: “A complex is a molecular entity formed byloose association involving two or more component molecular entities(ionic or uncharged), or the corresponding chemical species. The bondingbetween the components is normally weaker than in a covalent bond. Ininorganic chemistry the term “coordination entity” is recommendedinstead of “complex” (IUPAC inorganic NOMENCLATURE (1990).” See,http://www.chemicool.com/definition/complex.html.

The definition of“chelate”: “In reality, a chelate is any metal that isattached to an anion (negatively charged group) with more than oneattachment site. Chelation means that the anion has two or more separatesites to which the metal is bonded.” See, www.jostchemical.com.

The definition of a “dopant”: a dopant is “an impurity added usually inminute amounts to a pure substance to alter its properties.” See,www.merriam-webster.com/dictionary/dopant. According towww.freedictionary.com, under “medical” the term “to dope” is used inmaterials sciences as a verb which means “To add or incorporate asubstance or other additive to a chemical compound of interest, with theintent of improving or altering performance parameters.”

The definition of“fixed copper”: a copper compound which is insoluble orhighly insoluble in water. Fixed Coppers are further disclosed by H.Wayne Richardson in the “Handbook Of Copper Compounds And Applications”,page 97 third paragraph, “suitable copper compounds include fixedcoppers [Cu+(OH)2], Bordeaux, as well as other well known fixed coppercompositions including those disclosed in CRV Handbook of PestManagement in Agriculture, Vol. 3, David Pimentel (editor), CRC Press,Boca Raton, Fla. (1981), which is incorporated herein by reference” andSabin '196 patent such as copper oxide/cuprous oxide, copperoxychloride, tribasic copper sulfate (CuSO₄ 3Cu(OH)₂, copper diammoniadiacetate complex and/or any other well-known fixed or insoluble coppercompositions currently being used, or has been prior used as apesticide, fungicide, bactericide, and algaecide. Exemplary examples arecopper hydroxide, copper/cuprous oxide, copper carbonate, copperoxychloride, basic carbonate, copper carbonate, basic copper sulfatesincluding particularly tribasic copper sulfate, copper oxychlorides, andmixtures thereof; ammonia copper carbonate, basic copper chloride, andothers, and mixtures thereof.

The term “iron doped copper hydroxide” refers to a copper hydroxidecompound that is doped with an iron compound. It is understood inalternate embodiments that the copper hydroxide compound may besubstituted with another fixed copper compound as provided herein.

The term “zinc doped copper hydroxide” refers to a copper hydroxidecompound that is doped with a zinc compound. It is understood inalternate embodiments that the copper hydroxide compound may besubstituted with another fixed copper compound as provided herein.

The term “zinc and iron doped copper hydroxide” refers to a copperhydroxide compound that is doped with both an iron compound and a zinccompound. It is understood in alternate embodiments that the copperhydroxide compound may be substituted with another fixed copper compoundas provided herein.

Examples of iron compounds include any insoluble or substantiallyinsoluble iron compound. Further examples include, but are not limitedto iron compounds selected from the group consisting of iron hydroxide,iron oxyhydroxide, iron oxide, iron glucose, ferric citrate, Ferritin,ferrous fumarate, and ferrous sulfate. Most preferably the iron compoundis iron hydroxide and/or iron oxyhydroxide.

Examples of zinc compounds include any insoluble or substantiallyinsoluble zinc compound. Further examples include, but are not limitedto zinc compounds selected from the group consisting of zinc hydroxideand zinc oxide.

In a preferred embodiment, the term “insoluble or substantiallyinsoluble” is used herein. However, based on industry standards,Applicant submits that there is not a hard and fast quantitativedefinition for such terms as used by those of skill in the art.Accordingly, terms such as “sparingly soluble”, “insoluble”, “highlyinsoluble”, “slightly soluble”, (“negligible”) etc. have been used fordecades by those of skill in the art. See, for Example U.S. Pat. No.5,385,934, at column 1, lines 28-38, wherein Professor Emeritus MiltonN. Schroth provides that “These copper based compositions are typicallyaqueous“fixed” copper based compositions because the copper compoundsused in these compositions typically have a solubility of free Cu+2 fromabout 1 to 30 ppm in the aqueous solution with the remainder (and thevast majority) of the copper either being insoluble or in chelated form(i.e., “fixed”). The 1 to 30 ppm of Cu+2 in such aqueous compositions istypically referred to as “free copper” to distinguish it from either thechelated Cu+2 or the insoluble Cu+2 in these fixed copper compositions.”Similarly, Professor Santra discloses in U.S. Pat. No. 8,221,791 B1 “Animportant consideration is whether to use “soluble” or “insoluble”copper(Cu) for long term fungicidal or bactericidal protection. The“soluble” Cu refers to Cu based salts (such as Cu sulphate) thathydrolyze completely in water, producing ionic Cu. The “insoluble(sparingly soluble) Cu compounds act as a reservoir from which Cu ion isreleased to the plant surface on which it is deposited uponapplication.” Additionally, Professor Santra provides “Currently used Cucompounds possess unique set of physical and chemical properties. Theydiffer in their total amount of metallic Cu content and aqueoussolubility. It is well understood that the antibacterial activity willdepend upon the availability of soluble (free and reactive) Cu ions inthe formulation. Among the existing Cu compounds, tribasic Cu sulphatesand cuprous oxide are least soluble, whereas Cu hydroxides are moresoluble than Cu oxychloride.” And Professor Santra further provides“Several Cu compounds are registered in the United States for managementof over 100 diseases on almost 50 food crops. The Cu compounds exhibitvarying degrees of effectiveness for any target organism on any givenhost. The most common forms of Cu that satisfy these conditions tovarying degrees are the normal hydrolysis products of Cu(1) and Cu(2)salts (also known as “insoluble Cu” of “fixed Cu” compounds: Cu(1)oxide, (Cu₂0), Cu(2) oxychloride(CuCl₂.3Cu(OH)₂), tribasic Cu(2)sulphate(CuSO₄3Cu(OH)₂, and Cu hydroxide(Cu(OH)₂.” In Agrochemical andPesticide Safety Handbook, Michael F Waxman discloses “Since copper istoxic to plants, it must be used at low levels or in the insoluble form.For this reason, the relatively insoluble or “fixed” copper salts areused. These compounds release copper ions at very low rates that areadequate for fungicidal activity but not at concentrations that wouldharm or kill host plant.” Richardson discloses “Alternate products weredeveloped primarily in the twenties and thirties and relied on lowsoluble or fixed coppers which could be applied as dusts or suspensions”and “A copper compound must be chosen that is relatively resistant toweathering and supplies enough copper to be toxic to the fungal sporesand bacterial cells without adversely affecting the host. The mostcommon forms of copper that satisfy these conditions to varying degreesare the normal hydrolysis products of copper(1) and copper(2) salts:copper (1) oxide(Cu2), cuprous oxide), copper(2)oxychloride(CuCl₂.3Cu(OH)₂, tribasic copper(2) sulphate(CuS0₄.3Cu(OH)₂,and copper hydroxides(Cu(OH)₂). These “fixed coppers” offer advantagesof application and reduced phytotoxicity over the classic Bordeauxmixture. “These are the terms Richardson uses: Pg 85, Copper(2)Phosphate Trihydrate, “insoluble in cold water”, Pg 55, Copper(1) Oxide,“virtually insoluble in water” Copper(2) oxide, Pp. 57, 58, “essentiallyinsoluble in water”, Pg 61, Copper(2) Hydroxide, “virtually insoluble inwater”, Pg 63, Copper(2) carbonate Hydroxide, “virtually insoluble inwater”, Pg 69, Copper(2) Oxychloride, “essentially insoluble in water”,Pg 79, Basic Copper(2) sulphate, “insoluble in water”, Pg 83, Copper(2)Gluconate, “soluble in water.” Richardson discloses a multitude ofCopper compounds and descriptive nomenclature describing theirsolubility as above demonstrated.

Those of the skill in the art can readily and easily test to determinethe lower doses required of the applicants invention to achieve diseasecontrol, and the doses to achieve disease control on copper resistantpathogens by standard routine testing.

The iron doping of the copper hydroxide nanoparticles is from a tracecontamination of iron, less than 0.01 at %, to about 40 at % iron withabout 5-15 at % elemental iron preferred, with about 15 at % elementaliron the most preferred quantity. Other fixed coppers may incorporatemore than 40 at % iron and/or zinc. While a variety of processes may beused to manufacture the doped component of the present invention,Applicant has used a wet chemical process as further indicated in detailbelow. It is understood to those of skill in the art that the processdisclosed herein is scalable for commercial production. The product isdried/evaporated by methods well known to those skilled in the chemicalart, and may be overcoated, if desired, with a stabilizer by methodswell known to those in the chemical art. For example, See U.S. Pat. No.4,404,169 to Ploss, et al. entitled “Process For Producing CupricHydroxide.” The preferred size of an iron doped copper hydroxidenanoparticle is sub-micron, from about 0.5 nm to 30 microns. A morepreferred size is from about 3.5 nm to 15 microns, an additionalpreferred size is from about 3.5 nm to 200 nm. A most preferred size isfrom about 3.5 nm to 10 nm, especially for both leaf protectorant andsystemic activity all in one. Different sizes may be mixed together inthe practice of the invention.

Moreover, fixed copper compounds, such as copper hydroxide, aregenerally insoluble or highly insoluble in water. While not beinglimited, held or bound to any particular theory or mechanism of action,it is generally thought that “The free copper penetrates into thebacterial and/or fungal micro-organism in order to exert its toxiceffect.” (See U.S. Pat. No. 5,202,353 of Schroth, Iron Enhancement ofCopper Based Fungicidal and Bactericidal and Bactericidal Compositions,1993). Applicant believes, in addition, that the generation of reactiveoxygen species (ROS) by fixed copper compounds and the additionalincrease in ROS generation with the addition of an iron compound ispesticidal. Moreover, while not being limited held or bound of anyparticular theory or mechanism of action, it is thought that exudates onthe surfaces of the plant leaves, taken together with the rainfall andthe acidic rain, produce an acidic environment which dissolves the fixedcopper compounds and releases free copper, which is very active againstpathogens.

Thus without being limited, held or bound to these plant diseasesdisclosed, there are hundreds and hundreds of plant diseases amenable tocontrol by copper pesticides and that the applicant's invention willsurely potentiate the biocidal effects of copper pesticides againstthese pests. The composition of the present invention may be used withany known biologically inert carrier, including, but not limited to, aliquid diluent, e.g., water, a solid diluent and/or a surfactant. Thecomposition of the present invention is designed to be compatible withthe physical properties of copper hydroxide and any other activeingredients, method of application and environmental factors which mayinclude soil type, moisture and temperature, organic matter, soilstructure, current nutrient levels and more, well known to those in thechemical and agricultural art.

Moreover, without being limited held or bound to any particular theoryor mechanism of action, the more iron added to the copper hydroxide orother fixed copper, the more biocidal/robust pesticide the inventionwill be toward pests.

Moreover, in one embodiment of the present invention herein, Applicant'siron doped copper hydroxide, or zinc doped copper hydroxide, or zinc andiron doped copper hydroxide, in an optional embodiment, may bestabilized or overcoated. U.S. Pat. No. 4,404,169 Ploss, et al.discloses methods of stabilizing compounds of the applicant's invention.Overcoating, can modulate release of the active ingredient.

In an alternate embodiment, insoluble iron compounds, such as ironhydroxide or iron oxyhydroxide, may be added to copper hydroxide so thatthere are two separate components. In a further alternate embodiment,iron hydroxide or other insoluble iron compounds, may be added to theiron doped copper hydroxide, so there are also two separate components.In each case, everything goes together in the spray tank foragricultural uses.

Moreover, since iron and copper are recognized micronutrients,recognized by the American Society of Agronomy and the Soil ScienceSociety of America, then it follows that the remaining micronutrientsboron, chloride, manganese, molybdenum and zinc, can easily be added tothe iron or zinc or iron and zinc doped copper hydroxide, which usesiron and or zinc as a dopant to produce a doped copper hydroxide ironfungicide/bactericide/nutrient with micronutrients for foliar, trunk,branch and/or root application and/or injection in the trunk or branchesof the plant. Moreover, secondary nutrients such as calcium, magnesiumand sulfur may also be added, singly or together in combination.

Applicant's invention is the only known foliar nutritional bactericidalformulation that enters the phloem and kills the HLB disease causingCandidatusLiberibacter (CLas) bacteria.

Since zinc has established anti-microbial activity against bacteria,fungi and other pathogens, Applicant proposes to potentiate, increaseactivity of the claimed iron doped copper hydroxide by further dopingthe copper hydroxide with a zinc compound so that the end product willbe an iron doped, zinc doped copper hydroxide or other fixed copper. Itis understood that the doping with zinc is provided by a zinc compoundand not by the use of pure metallic zinc, an element.

Preferred embodiments of this invention include both a zinc compounddoped copper hydroxide and an iron compound doped copper hydroxide. Zincsulfate is an exemplary example of a zinc salt thought to be useful inthe manufacture of compounds of the invention. The sulfur in zincsulfate is also a plant nutrient. Applicant also claims copper hydroxidewhich is both doped with an iron compound and a zinc compound together.In the preparation of the iron doped copper hydroxide, excess iron morethan that the copper hydroxide will incorporate, is left in thepreparation, so that the upshot is iron doped copper hydroxide, withadditional iron hydroxide, in the preparation thereof. It may very wellbe an iron oxyhydroxide or other iron compound incorporated in thedoping process.

Iron doped copper hydroxide, with and without additional unincorporatediron hydroxide in the preparation, may be combined with zinc dopedcopper hydroxide with and without additional unincorporated zinchydroxide or other zinc compounds, and both zinc and iron doped copperhydroxide with both additional unincorporated zinc and iron may also allbe used in combinations or mixtures thereof. Other useful compounds areferrites, which may be an additional alternate compound to be used standalone, or may be combined as the iron and/or zinc doped copper hydroxideis also used. A ferrite is a type of ceramic compound composed of ironoxide (Fe₂O₃) combined with one or additional metallic elements inchemical combination. See Encyclopedia Britannica. See Wikipedia.Exemplary examples are copper zinc iron oxide (CuZnFe₂O₄). See Sigmaorder confirmation, order date Apr. 6, 2015, order number 3013972345.This order also contains a copper iron oxide ferrite (CuFe₂O₄). SeeSigma Technical Services answer of Jeanne Harrell, “X-ray DiffractionResults”, dated Apr. 14, 2015. Other ferrites include zinc iron oxidenanopowder (ZnFe₂O₄). See American Elements 150416RP03, dated Apr. 14,2015. Another ferrite is a copper ferrite (CuFe₂O₄). See AmericanElements data sheet for copper ferrite, dated Apr. 16, 2015. There maybe manganese in the composition of useful ferrites. While not beinglimited, held or bound, the aforesaid ferrites are exemplary examplesthought to be useful in the practice of the invention, and may becombined in any combination with themselves or other compoundspreviously disclosed in the practice of the invention. Preferably, thesize of the ferrites are from 0.5 nm up to 30 microns.

These combinations or mixtures thereof are easily tested againstbacteria, fungi, viruses, mycoplasma and other pathogens, by rapid, wellestablished, routine testing well known to those skilled in the art,such as laboratory high throughput screening of vast numbers ofcompounds in vitro, and/or greenhouse plantings.

The compositions of the Applicant's invention are especially directedand exquisitely suited as a treatment for Huanglongbing (HLB) disease ofcitrus, and citrus canker, and other citrus diseases, such as GreasySpot, Melanose, and Alternaria Brown Spot, where copper is currentlyutilized. Applicant's doped composition of fixed coppers doped withzinc, iron, or both, are also useful in treating banana plants afflictedwith Black Sigatoka disease, Yellow Sigatoka disease and Panama disease.

Moreover, the small size of Applicant's invention will improve foliagecoverage of leaves, which is well known in the art, that smallparticulates provide more uniform and superior coverage to leaves ofplants. A critical and distinguishing feature of the Applicant'sinvention is that in preferred embodiments it can be an ultra-smallinsoluble copper and iron compound. Moreover, another critical aspect ofApplicant's invention is the size of Applicant's iron doped copperhydroxide such that it is enabled for systemic uptake of the copper andiron. This size of Applicant's particles is unlike any size of anycommercial fixed copper, so far as the Applicant is aware of; tofacilitate systemic administration. Applicant's particulate at about90+% particulate, is about 3.5 to 10 nm, as both a leaf protectorant anda systemic pesticide, and bactericide. Previous insoluble or fixedcoppers are not systemic due to their large size for the most part.Applicant's particulate is about 90+% approximately 3.5 to 10 nm, inorder to avoid aggregation, and has the best chance to facilitatesystemic uptake. Preferably, Applicant's invention is to be administeredwith adjuvants/surfactants. Applicant's Transmission Electron Microscopy(TEM) image of FIG. 2 herein was tested with a surfactant, to insuregood separation. Typical surfactants thought to be useful for theApplicant's invention are described in Silwet Adjuvants and SAGAntifoams for Agricultural Applications, (2012), published in Momentivepublication of Momentive Performance Materials, Inc. of Albany, N.Y. and“Adjuvants Products Guide” of Nufarm.

In the foregoing description, certain terms and visual depictions areused to illustrate the preferred embodiment. However, no unnecessarylimitations are to be construed by the terms used or illustrationsdepicted, beyond what is shown in the prior art, since the terms andillustrations are exemplary only, and are not meant to limit the scopeof the present invention. Other fixed coppers may also be, joined,doped, with iron compounds and/or zinc compounds to practice theinvention. Therefore, it is understood that Applicant's use of copperhydroxide for the fixed copper compound may be readily substituted withother known fixed copper compound. Copper hydroxide and other fixedcoppers may be doped with insoluble iron compounds, and/or withinsoluble zinc compounds.

Moreover, because of the ultra-small size of the doped components in theApplicant's invention, at approximately 3.5-10 nm, it has been shownthat copper hydroxide plus the adjuvant/superspreader Silwet-77 is toxicto the Asian Citrus Psyllid nymphs, a vector of bacterial HLB.Applicant's invention, with the addition of zinc (Zn) and iron (Fe), isthought to further enhance the pesticide efficacy of copper hydroxide orother fixed coppers against this vector/carrier of HLB bacteria, andadult vector/carrier Psyllid nymphs.

The upshot is that doped components of the Applicant's invention hitsthe bacterial causes of HLB disease and Xyella fastidiosa infection ofOlive Trees, and other external/internal plant pathogens in at leastthree ways at the least, as follows:

a) as a leaf protectorant with supra fine particle size; i.e. 3.5-10 nm;

b) as a leaf and systemic pesticide bactericide/fungicide; i.e. 3.5-10nm; and,

c) as a pesticide against vector/carrier of HLB bacteria, the AsianCitrus Psyllid nymphs and adults, and sharpshooters, froghoppers, andspittlebugs, vectors of XyellaFastidosa. Additionally, Applicant'sinvention simultaneously treats citrus canker and other citrus diseases.

In one embodiment of the present invention, the doped component is afixed copper compound doped with magnesium and/or calcium.

Moreover, compounds of the Applicant's invention may be used with agentswhich currently synergizes with copper administration, such as forexample Regalia biofungicide, and horticultural oils, and pesticidaladjuvants such as Silwet-L77, and other pesticides.

Compounds of the present invention are suitable for the customaryadjuvants and formulation aids, which include but not limited tosurfactants, wetting agents, stabilizers, dispersants and anti-foamagents.

Applicant claims iron compounds doped into copper hydroxide preferablyiron hydroxide or iron oxide, zinc compounds doped into copper hydroxidepreferably zinc oxide, iron compounds and zinc compounds doped togetherin copper hydroxide. These doped copper hydroxide compounds may becombined in any combination, or mixtures thereof and additional ironcompounds, e.g. iron hydroxide, or zinc compounds, e.g. zinc oxide, maybe added. For example, iron hydroxide doped copper hydroxide at 15 at %iron may have free unincorporated iron hydroxide with it at 5, 10, 15,20, 25, 30, 35 at % iron hydroxide or more together with the 15 at %iron hydroxide doped copper hydroxide. Applicant claims all fixed coppercompounds doped with iron compounds and/or zinc compounds foragricultural pesticidal usage.

EXAMPLES

The following examples illustrate the invention without limiting it.Except where otherwise indicated, the parts and percentages shown areexpressed by percentage (at %).

Example 1 Synthesis of Iron-Doped Conner Hydroxide

Iron-doped Copper Hydroxide (Fe—Cu(OH)₂) composite powder is synthesizedusing a wet chemical process. The starting materials for the synthesiswere copper nitrate hexahydrate(Cu(NO₃)₂.6H₂O), iron chloride (FeCl₃),sodium hydroxide (NaOH) and deionized water (H₂O). To synthesize ˜15 at% Fe-doped-Cu(OH)₂, 2.43 g of copper nitrate hexahydrate and 0.4 g ofiron chloride were dissolved in 75 mL of deionized water in a roundbottom flask. The solution was refluxed for 3 hours. Once the solutioncooled down to room temperature, 102.2 mL of 0.25 M NaOH was added. ThepH at this stage was between 10 and 11. Subsequently, the solution wastransferred to a beaker and another 102.2 mL of NaOH was added, whilestirring the solution, using a high shear mixer at ˜1000 rpm. The pHafter the addition of NaOH was between 11 and 12. The precipitate waswashed one time using deionized water and finally dried in air. Similarmethods were used to synthesize iron-copper hydroxide composite, wherethe amount of iron was varied from 20 to 50 at %.

FIG. 1 is an X-ray diffraction test verifying that copper hydroxide isdoped with an insoluble iron. In connection therewith, in FIG. 2 herein,Applicant submits a data sheet of Applicant's iron doped copperhydroxide with 15 at % iron elemental analysis of FIG. 3. FIG. 2,discloses Applicants invention tested out by TEM at about90%+particulates, which is a very narrow particulate distribution unlikeany other commercial product, between 3.5 nm and 10 nm. FIG. 4 is theX-ray diffraction of 15 at % Iron doped+additional 10 at % Iron that thecopper hydroxide is unable to incorporate, so that the final preparationis 15 at % Iron doped copper hydroxide+10 at % unincorporated/free IronHydroxide and or Iron Oxide.

Example 2 Synthesis of Iron-Zinc-Doped Copper Hydroxide

Iron-Zinc-doped Copper Hydroxide (Fe—Zn—Cu(OH)₂) composite powder issynthesized using a wet chemical process. The starting materials for thesynthesis is copper nitrate hexahydrate (Cu(NO₃)₂.6H₂O), iron chloride(FeCl₃), zinc sulfate heptahydrate (ZnSO₄.7H₂O), sodium hydroxide (NaOH)and deionized water (H₂O). To synthesize ˜7.5 at % Fe-7.5 at %Zn-doped-Cu(OH)₂, 2.43 g of copper nitrate hexahydrate, 0.21 g of zincsulfate heptahydrate and 0.19 g of iron chloride is dissolved in 75 mLof deionized water in a round bottom flask. The solution is refluxed for3 hours. Once the solution cools down to room temperature, 102.2 mL of0.25 M NaOH is added. Subsequently, the solution is transferred to abeaker and another 102.2 mL of NaOH is added, while stirring thesolution, using a high shear mixer at ˜1000 rpm. The precipitate iswashed one time using deionized water and finally dried in air. Thesimilar method is used to synthesize other variations ofiron-zinc-copper hydroxide composite.

Example 3 Synthesis of Zinc-Doped Copper Hydroxide

Zinc-doped Copper Hydroxide (Zn—Cu(OH)₂) composite powder is synthesizedusing a wet chemical process. The starting materials for the synthesisis copper nitrate hexahydrate (Cu(NO₃)₂.6H₂O), zinc sulfate heptahydrate(ZnSO₄.7H₂O), sodium hydroxide (NaOH) and deionized water (H₂O). Tosynthesize ˜15 at % Zn-doped-Cu(OH)₂, 2.43 g of copper nitratehexahydrate, 0.42 g of zinc sulfate heptahydrate is dissolved in 75 mLof deionized water in a round bottom flask. The solution is refluxed for3 hours. Once the solution cools down to room temperature, 102.2 mL of0.25 M NaOH is added. Subsequently, the solution is transferred to abeaker and another 102.2 mL of NaOH is added, while stirring thesolution, using a high shear mixer at ˜1000 rpm. The precipitate iswashed one time using deionized water and finally is dried in air. Thesimilar method is used to synthesize other variations of zinc-copperhydroxide composite. The Applicant preferably has used additional zincsulfate heptahydrate, so that the finished synthesis contains zinc dopedcopper hydroxide plus unincorporated zinc oxide alone, in the finishedpreparation.

Use of Compositions for Treating Black Sigatoka Disease. Yellow SigatokaDisease and Panama Disease in Banana Crop Plants:

The Applicant's agricultural pesticides used to treat agricultural cropsaffected with vascular crop diseases such as Huang-longbing bacterialdisease in orange crop plants or Xylella fastidosa disease in olive treecrop plants, namely with zinc or iron-doped copper hydroxide singly ortogether, and/or with ferrites, are exquisitely also suited for fungaldiseases of banana, especially the three leading banana killersworldwide, namely Black Sigatoka disease, Yellow Sigatoka disease andPanama disease.

Bananas are a staple for an excess of 400 million subsistence people inthe tropics. They are under vicious critical attack by these fungaldiseases. See Mourichon et al, Sigatoka Leaf Spot Diseases, PROMUSAWorking Group, International Network for Improvement of Banana andPlantain Montpellier Cedex, FR,www.biodiversityinternational.org/uploads/tx_news/Sigatoka_leaf_spot_diseases_699.pdfOctober, 1997, which discusses Black Sigatoka disease, also known asBlack Leaf Streak disease (BLSD) caused by the ascomycetous fungiMycosphaerella fijiensis Morelet, as well as Yellow Sigatoka disease,also known as Sigatoka disease (SD), caused by the ascomycetous fungi M.musicola Leach x Mulder. Mourichon et al also discuss the fact thatsystemic topical spraying of fungicides is a cause of environmentalconcern, and that the fungi grow resistant to conventional fungicides.See Ramaker, “Banana disease continues to Spread”,resource.wageningenur.nl, Nov. 26, 2015, showing aerial photos depictingwidespread destruction of banana plants in a banana plantation. Ramakerstates that there is widespread destruction of banana plants in theMiddle East, Southeast Asia, East Africa and Australia affected byPanana disease of banana plants. Ramaker also states it is only a matterof time before it spreads to South America. Ramaker notes that effortsto quarantine afflicted banana plants have failed to stop the spread ofPanama disease in banana plants. Ramaker notes that the Panana diseasecausing fungus Fusarium oxysorum survives in the soil for long periodsof time, even after afflicted banana plants are removed. See “BananaCultivation” of Wageningen; see “Black Sigatoka of Banana: The mostimportant disease of a most important fruit” of Randy Ploetz. BlackSigatoka is the most important banana disease, opus cited, see “PlantHealth Australia Fact Sheet.” See also Outrageous Minds publicationarticle, “Banageddon: Millions face hunger as Panama disease and BlackSigatoka decimate global banana crop” and see also “Black Sigatoka: AnIncreasing Threat to Banana Cultivation” Douglas H Marin, et al.

Black Sigatoka is currently being treated with systemic fungicides whichare failing. See Douglas H. Marin et al. Opus cited. In a personalcommunication with one of the authors above, Turner Sutton discloses“Copper fungicides have been used for Sigatoka control, especially inthe past there was a heavy use of Bordeaux mixture followed by othercopper based formulations. Because of the heavy use of copper in thepast it accumulates in the soil at phytotoxic levels. This, and thedevelopment of new protectant products discouraged the use of Copperfungicides. Additionally, with the introduction of agricultural oil,some copper formulations react with the oil causing phytotoxicity on theleaves.” As this article discloses these systemic fungicides arebecoming inactive due to mutations and chemical resistance. This hasonly gotten worse since the time of the article in 2003. See “BlackSigatoka” by Randy Ploetz, which discloses that fixed coppers were theold standard methods until the systemic fungicides, beginning withBenomyl. Resistance has developed with these systemics with challengesahead for control of Black Sigatoka disease in banana crops. Accordingto Mourichon et al, supra, Yellow Sigatoka disease is also prone topesticide resistance. Because of the wet conditions where bananas aregrown (see Table 1, Randy Ploetz in “Disease Control”), this hasnecessitated up to about 50 sprayings weekly, with costly environmentaldamage, labor and capital intensive administration of these fungicides,which adds about 25% to the cost of banana production see “Top Banana”at Martinez page 5.

“Copper completes the circle for Sigatoka control” by Terry Mabbett,which discloses that “Copper fungicide has travelled the complete circlein the control of Sigatoka disease on banana. Copper was the very firstfungicide to be used against yellow Sigatoka over 60 years ago and isnow back in contention and favour due to its broad spectrum activity andlong history of use without resistance which now plagues manysingle-site systemic fungicides.” See Mabbett also “Copper makes a fullcircle” at page 221, and “Positive profile for copper fungicide” on page221, and “Rise and fall of systemic fungicides” at page 222.

It is further noted that all existing fixed copper fungicides are “cropprotectants” and do not enter the systemic vascular circulation of thebanana plant, and therefore are inactive after a banana plant has becomeinfected. The fixed copper fungicides as crop protectants kill thisSigatoka Disease fungus spore on the leaf and block its entry throughthe stoma into the leaf. See Bennett et al, Black Sigatoka of Bananasand Plantains, p. 6, Cornell University,www.apsnet.org/edcenter/intropp/lessons/fungi/ascomaycetes/Pages/BlackSigatoka.aspx,2003.

In contrast to known fungicides, Applicant's invention with itspreferred 5-10 nm size will enter the banana leaf through the stoma, orby other means, which is referred to being “locally systemic”, tocounter the fungus systemically affecting the afflicted banana plant.Simultaneously, the compositions of Applicant's invention act like otherclassical fixed coppers, as a crop protectant on the surface of theleaf. Moreover, the compositions of Applicant's invention is used toreduce the number of sprayings due to wet weather, because of itssystemic activity like the prior systemics, which were unsuccessfullyused to try and control Black Sigatoka disease or Yellow Sigatokadisease in banana plants. Moreover, as Ploss, in U.S. Pat. No.7,105,136B2, has shown in his '136 patent, inferentially, because of thesystemic activity of nano copper hydroxide in using Applicant'sfungicidal compositions, only a fraction of the quantity of thepreviously used copper hydroxide will be needed, to be effective.

Moreover the Applicant's supercharging by doping of copper hydroxide,copper oxide or other fixed coppers, with zinc or iron, or both, furtherstrikingly increases functional activity and reduces copper usage, thusfurther mitigating the harmful effects of excess copper accumulation inthe soil. Moreover both the iron and zinc are recognized establishedmicronutrients to simultaneously feed the banana plant.

The Applicant notes that “Pesticides Registered for Use in Banana inHawaii” of EPA reg. no. Sep. 2, 2014, Hawaii Department of AgriculturePesticides Branch; National Pesticide Information Retrieval System(NPIRS) Purdue University, shows ten different prior art copperhydroxide formulations, which were approved to treat Black and YellowSigatoka in bananas plus another five copper formulations. However,every one of those ten prior art different copper hydroxide formations,is a crop protectant with particles too big to enter the leaf site ofinfection, and therefore are incapable of being systemic in thevasculature of the banana plant. In “Control of black Sigatoka disease:Challenges and Prospects” by Ebimieowei Etebu, at page 510, Etebu statesas follows: “Protectants were the first group of fungicides that werediscovered and used in crop protection. They are non systemic, and assuch do not penetrate plant tissue. Protectant fungicides do not controlfungi that are already established within the plant tissues since theydo not penetrate the plant tissues themselves.”

The Applicant's fungicidal compositions are distinguished from the priorart by their unique doping with zinc and/or iron, singly or together,and with a unique small size, capable of entering the banana plant leaf,the site of infection.

Panama disease s another blight affecting afflicted banana plants.Panama disease is caused by a fungus Fusarium oxysporum f sp. cubense(Foc), which, along with Black Sigatoka are the two grievous existentialthreats to banana crop production and the lifeblood of over 400 millionsubsistence banana crop farmers. Panama disease is a vascular funguswhich can remain active in the soil for many decades and it cannot befully controlled by prior art fungicides. There is a desperate need fortreatment for Panama disease. See “YES WE HAVE NO BANANAS: The world'sfavorite fruit is slowly but surely being driven to extinction” by GwynnGuilford in Quartz; See also “Yes! We have no bananas? It could actuallyhappen” Mark Koba; see “Fungus Threatens Banana Supply” Mark Koba; seealso “Worse Comes to Worst: Bananas and Panama Disease—When Plant andPathogen Clones Meet” Nadia Ordonez in PLOS Pathogens.

Applicant's fungicidal compositions, with their small size suitable forsystemic uptake, in the banana plant, and the proven anti-fungalcharacteristics of the fixed coppers i.e. copper hydroxide, plus beingdoping with iron and/or zinc, make Applicant's compositions verydesirable for the treatment of Panama disease.

Moreover, fixed coppers, i.e. copper hydroxide, are approved for manyother banana diseases, i.e. Black pitting, see “Pesticides Registeredfor Use in Banana in Hawaii” (Sep. 2, 2014). In point of fact, copperhydroxide is recommended for “Bananas, Beans, Cabbage, Cacao, Carrots,Cauliflower, Celery, Citrus, Coffee, Cucumber, Grapes, Onion, Peas,Peanuts, Pepper, Potato, Rice, Tomato and Watermelon” see “Fungicides”Jocanima Corporation. In fact, copper is approved in dozens of plantdiseases, bacteria, fungi and viruses, see Denis Rusjan (2012). “Copperin Horticulture, Fungicides for Plant and Animal Diseases”, Dr.Dharumadurai Dhanasekaran (Ed.). pp. 257-278.

However, despite the limited success of the aforementioned copper basedtreatments for treating banana crop plants afflicted with Black Sigatokadisease, Yellow Sigatoka disease, or Panama disease, in contrast,Applicant's doped fixed coppers compositions, which are doped with zinc,or iron, or both, or, alternatively, Applicant's ferrite compositions,are uniquely capable of systemically or effectively capable of treatingbanana crop plants afflicted with “Panama” disease, “Yellow Sigatoka”disease and “Black Sigatoka” disease, while minimizing the accumulationof copper in crop soils.

Although the present invention has been disclosed in terms of apreferred embodiment, it is further known that other modifications maybe made to the present invention, without departing from the spirit andscope of the invention.

I claim:
 1. A pesticide composition to be applied to banana crop plants,wherein said composition is effective in treating banana plantsafflicted with Black Sigatoka disease, Yellow Sigatoka disease andPanama disease, comprising: a) at least one biologically inert carrier,and b) at least one ferrite containing copper, zinc or iron alone, or inany combination, and, c) optionally at least one doped componentcomprising at least one fixed copper compound doped with at least onecompound selected from the group consisting of iron compounds, zinccompounds and combinations thereof; d) said pesticide composition to beapplied to agricultural plants in an effective amount for the treatmentof agricultural crop diseases.
 2. The pesticide composition according toclaim 1 wherein said ferrite is iron oxide.
 3. The pesticide compositionaccording to claim 1 wherein said ferrite is copper zinc iron oxide. 4.The pesticide composition according to claim 1 wherein said ferrite iscopper iron oxide.
 5. The pesticide composition according to claim 1wherein said ferrite is zinc iron oxide.
 6. The pesticide compositionaccording to claim 1, wherein said fixed copper compound is selectedfrom the group consisting of cupric hydroxide, copper oxychloride,copper oxide, cupric carbonate basic, copper sulfate basic, tribasiccopper sulfate, cuprous oxide, cupric citrate, cupric phosphate,cuprobam, indigo copper, minerals brochantite, langite, malachite,cometite, libethenite, pseudolibethenite, pseudo-malachite, antlerite,covellite, marshite, cuprite, chalcocite, Rogojski's salt, brochantite,hydrocyanite, nantokite, dolerophane, ammonia copper carbonate, basiccopper chloride, and combinations thereof.
 7. The pesticide compositionaccording to claim 6, wherein said fixed copper compound is cuprichydroxide.
 8. The pesticide composition according to claim 1, whereinsaid iron compound is an insoluble or substantially insoluble ironcompound.
 9. The pesticide composition according to claim 8 wherein saidiron compound is selected from the group consisting of iron hydroxide,iron oxyhydroxide, iron oxide, iron glucose, ferric citrate, Ferritin,ferrous fumarate, ferrous sulfate, and iron saturated humanholotransferrin.
 10. The pesticide composition according claim 1,wherein said zinc compound is an insoluble or substantially insolublezinc compound.
 11. The pesticide composition according to claim 10,wherein said zinc compound is selected from the group consisting of zinchydroxide and zinc oxide.
 12. The pesticide composition according toclaim 1, wherein said fixed copper compound is cupric hydroxide and saidiron compound is iron hydroxide and/or iron oxyhydroxide.
 13. Thepesticide composition according to claim 1, wherein said doped componentincludes about 15 at % iron from said iron compound doped within saidfixed copper compound.
 14. The pesticide composition according to claim1, wherein said particle size of said doped component is about 0.5 nm toabout 30 microns.
 15. The pesticide composition according to claim 1,wherein said doped component is only doped with an iron compound and/ora zinc compound.
 16. The pesticide composition according claim 1,further comprising c) at least one iron compound mixed with a) and b).17. The pesticide composition according to claim 16, wherein said ironcompound is at least one insoluble or substantially insoluble ironcompound.
 18. The pesticide composition according to claim 17, whereinsaid iron compounds is iron hydroxide.
 19. The pesticide compositionaccording to claim 1, further comprising d) at least one zinc compoundmixed with a), b) and c).
 20. The pesticide composition according toclaim 19, wherein said at least one zinc compound is an insoluble orsubstantially insoluble zinc compound.
 21. The pesticide compositionaccording to claim 20, wherein said at least one zinc compounds is zinchydroxide or zinc oxide.
 22. The pesticide composition according toclaim 1, further comprising d) at least one zinc compound mixed with a)and b).
 23. The pesticide composition according to claim 22, whereinsaid at least one zinc compound is an insoluble or substantiallyinsoluble zinc compound.
 24. The pesticide composition according toclaim 23, wherein said at least one zinc compounds is zinc hydroxide orzinc oxide.
 25. A method for the control of Black Sigatoka disease,Yellow Sigatoka disease and Panama disease in banana plants, comprising;applying to said pests or their growth habitat a pesticide compositionaccording to claim
 1. 26. The method according to claim 25, wherein saidpesticide composition is administered to said pests or their growthhabitat by a method selected from the group consisting of dusting,sprinkling, spraying, brushing, dipping, smearing, impregnating,injection of the composition into plant vasculature, and application toa root system.